Process for desulphurizing hydrocarbons



Oct. 8, 1935.

A. E. BUELL El AL PROCESS FOR DESULFHURIZING HYDROCARB'ONS Filed Sept. 10, 1932 FIG1.1. .FRACTIONATED TGASOLINE THROUGH BAUXITE.

FRACTIONATOR AFTER BAUXITE TREATMENT INVENTORS FIG. 2.

LC L m E T UC .A EAW Im Aw ?atented Oct. 8, 1935 PROCESS FOR DESULPHURIZING HYDROCARBONS Albert a. Buell and Walter A. Schulze, Battlesville, Okla assignors to Phillips Petroleum Company, Bartlesville, kla., a corporation of Delaware Application September 10, 1932, Serial No. 632,608'

6 claims.- ((31.196-28) The present invention is a continuation in part of the copending application,' Serial Number 616,574, filed June 10, 1932, for Processes of desulphurizing hydrocarbons, wherein it is shown. 6 that certain minerals constitute efiective contact agents for the vapor phase desulphurization of hydrocarbons by which a part of the organically combined sulphur is eliminated as hydrogen sulphide.

it) This invention relates to the application of one of the most. suitable of the several mineral contact agents disclosed in the said copending application, namely, bauxite, a mineral essentially composed of hydrated aluminum oxide, to v a process of desulphurizing petroleum oils, such as straight run and cracked gasolines, natural gasolines, hydrocarbon gases containing organic sulphur compounds, kerosene, and gasoline stocks or distillatesderived from oil shale or r from the decomposition of coal, etc. The invention relates further to a method of reactivating the bauxite after a decrease or loss of activity during use has taken place. It has 2 been found that the bauxite hasa greater catawhen new, and that this increase inactivity .is not due to dehydration, since the new bauxite is well dehydrated before it is used, as will hereinafter appear. The bauxite may be subsequently regenerated an indefinite number of times according to the process of the present'invention without noticeable decrease in' this enhanced catalytic activity. It has further been found that, as a contact agent for the desulphurization of petroleum vapors, the action of this activated bauxite is greatly superior to that of a true adsorbent clay, such as fullers earth, which is es- 4 lustrates a system wherein the cracked gasoline is fractionated prior to passage through the bauxite, while Fig. 2 illustrates a system wherein fractionation is eifected after the'bauxite treatment. 1

The treatment of straight run gasolines according to the process of the present invention is relatively simple, consisting merely of passing the gasoline vapors, superheated by any convenient means to temperatures between 550 and 750 F., preferably 650 ,F., through a bed of bauxite crushed to a convenient degree of finen'es'i. say 20-90 mesh to the inch or other meshgrades between these limits, such as 30-60, and contained in a well insulated tower. or catalyst 60 chamber. v

lytic activity following its first regeneration than,

The flow rate of the gasoline may vary between the limits of 5 to 20 barrels per hour per ton of bauxite, depending upon the original 8111-,- phur content of the gasoline and the final content desired. Several thousand barrels may be 5 treated per ton of bauxite before an appreciable loss in activity is incurred. Loss in activity may be denoted by a positive doctor test in the product, but the loss is gradual and substantial sulphur reduction still takes place after the product 10 ceases to be sweet. It is, therefore, optional whether the catalyst is reactivated at the time sweetening ceases or when suiiicient sulphur removal no longer takes place. The desulphurized straight run gasoline is then treated by any suitable method for removal of. hydrogen sulphide, and sweetened if necessary.v Sweetening is unnecessary if (1) the catalyst has n'ot been used too long before reactivation and (2) the flow rate of the gasoline over the catalyst has not 20 been too high.

In this desulphurization process the mercaptans in the gasoline are converted into hydrogen -sulphide andthe corresponding olefines. As long as the'catalyst has a high activity or the gasoline 25 flow rate is not excessive, the mercaptans are so completely converted to hydrogen sulphide that the gasoline gives a negative doctor test on removal'of the hydrogen sulphide. This is what is meant'by the term fsweet gasoline in the ex- 30 amples given below. It is possible, however, to obtain a sweet gasoline even when the activity of the catalyst has decreased to the point where a portion of the mercaptans get by undecom-' posed if the gasoline is given a final caustic wash. The caustic solution, while removing hydrogen 1 sulphide, will also remove these traces of mercaptans which are left in the gasoline and a sweet gasoline will be produced without resorting to one of the usual sweeting methods.

Treatment of cracked gasoline is essentially the same as straight run except that a somewhat higher temperature, 675-700 F., is preferred. Systems which may be used in this treatment are shown, by way of example, diagrammatically on thedrawing. Each system comprises essentially a cracking furnace 5, reaction chamber 2, evaporator j3, fractionator E, superheater-coil 5, catalyst chamber 6, cooler I, clay tower 8, polymer separator 9, condenser I0, outlet II to subsequent treating device and (Fig. 2) gas oil separator l2. The several courses taken by the materials being treated will be clear to those skilled in the art from thefiow lines shown on-the drawin'g.-

The catalyst chamber may be placed in the system, either following the fractionator, Figure 1, or immediately before the-fractionator, Figure 2. In the latter case a gas oilseparator, I 2, is

used to effect a partial separation of the gas oil 9 low the temperature of-the catalytic chamber to insure more complete removal of the heavy ends; and the issuing vapors may then be raised to the desired temperature before passage over the catalyst. Since a partial polymerization of highly unsaturated compounds in the cracked gasoline apparently takes place during the passage over the bauxite, producing a yellow color in the gasoline, the second arrangement mentioned above is particularly advantageous. The frac tionating tower, 4, effects a condensation of the higher boiling components of the treated-vapors along with the greater part'of the colored bodies formed in the catalytic step, this condensate again being charged "to the cracking unit, I. The removal of much of the color from the gasoline in this step makes the flnal treatment for color and gumn uch easier. If this latter treatment consists in passing the vapors over an adsorbent clay, such as fullers earth, the life of the earth will be greatly increased.

In the alternative procedure in which ,frac-f tionated gasoline is superheated and passed over desired temperature.

the bauxite, the vapors leaving the catalyst chamber, 6, may be subjected to any desired treatment for reducingcolor and gum without further fractionation, if desired, since the end point of the gasoline is not appreciably changed during the desulphurizing treatment.

In either of these procedures the vapors to be passed over the bauxite are heated either in the auxiliary superheater or returned to the furnace and reheated in a superheating coil, 5, to the The catalyst chambers, 6, are preferably'provided in duplicate for each unit as is common practice in vapor phase treating, so that one chamber may be reactivated or recharged-while. the other is in use.

Bauxite, as stated above, is essentially a hydrated aluminum oxide; hence, on heating to elevated temperatures much water is driven ofl. This water of hydration is not driven oil. graduall with increasing temperature, such as is the case with hydrated aluminum silicates of the type of fuller's earth, but very rapidly at a thre"hold temperature somewhere between 392 and 572 F. The following examples are typical for the removal of the .water .of hydration from several diflerent samples of bauxite in the presence of water vapor under one atmosphere pressure. A sample of a typical adsorbent clay of the hydrosilicate type is included for comparative purposes. 1 1

as the temperature is sufliciently high to prevent undue condensation of the vapors in the catalyst chamber. I

It'has been found that the bauxite gradually loses its catalytic activity with use and that this decrease is considerably more marked when cracked gasoline is passed over it than when jstraight 'run gasoline is treated; Therefore, a satisfactory method of regeneration of the bauxite is extremely important economically when the desulphurization of cracked gasolines and distillates is \mdertaken.

The present invention comprehends a simple method of regeneration which may more aptly be termed an activation, since the activity of the bauxite following the first regeneration according to the invention is considerably greater than that of the new material and the life is much longer. 7

The reactivation process consists in first steaming out the residual hydrocarbon vapors and then passing air and steam simultaneously through .the catalytic material. A temperature of 775- 850 F.'is preferred but it is possible to use both 'lowerand higher temperatures depending on the V natureof the carbonaceous materials which are to be removed. For example, wehave been able to completely; remove these objectionable bodies from some samplesof bauxite at temperatures notv exceeding 660 But in general, in order to obtain regeneration in a minimum time temperatures of the order of PIS-850 F. are preferred. Thereactivation may also be accomplished by "first steaming the catalyst and subsequently passing air over it, instead of using steam and air simultaneously as indicated above or, as far as reactivation alone is concerned, the steaming may be omitted altogether in certain cases. It has been found, too, that the catalyst can be partially regenerated with steam alone and its life some-. what extended in some cases, but since the full activity can be restored by such a simple method as described above, it isobviously desirable in most cases to use both steam and air.

Usually the quantity of carbonaceous matter in the reaction-chamber is not large and the heat developed in the oxidation can be readily carried away. In cases where over-heating is likely to develop, flue gas can be substituted wholly or in part for the air at least in the preliminary stages of the regeneration, and the temperature of the ingoing gases can be regulated as well to obtain proper regeneration.

The bauxite can be regenerated without removal from the reaction chamber by heating the Percent oi loss in weight of sample at Description of sample 122 F. 212 F. 392F. 572 F. 752 F- 932 F.

1 iii-km bauxite #1-- o. 286 o. 457 1101 22. 35 28.70 30. 08 2 Arkansas bauxite 0. 482 0. 756 1. l7 17. 99 22. 00 23. 29 3 Arkansas bauxite 0. 495 1. 07 1. 87 21. 48 26. 16 27. 15 4- Alabama bauxite I1 0. 492 1. 25 1. 90 18. 31 21. 92 22. 98 5 Olmstead fuller's earth 0. 449 2. 60 6. 34 7. 94 8. 69

Therefore, in practicing this desulphurization process, the first step usually preferred consists in dehydrating the bauxite, preferably. in situ,

by raising the temperature gradually to approxlmately 752 F., while 'a slow stream of air or hydrocarbon gas is passed-over it, This step'of passing air" or hydrocarbon gas over the bauxite can-obviously beomitted. ifdesired, and the ,gasoline'vapors started over thc'bauxite'as soon ingoing air and steam to the necessary temperature or it can be removed to a'separate furnace for regeneration.

The bauxite, whether new or reactivated, gradually loses its activity during use and, as mentioned before, the decrease is more rapid when unsaturated hydrocarbons are present in the vapors passed over the catalyst. The desulphurization of the gasoline vapors, however. is so complete with respect to mercaptans when the bauxite is not poisoned with impurities that a negative doctor test is obtained after the hydrogen ulphide is removed. Experiments on Panhan e straight run gasoline show that the first 2,000

barrels of gasoline per ton of bauxite can be obtained sweet to the doctor test. Also, the tests on Panhandle cracked gasoline show that at least 500 to 800 barrels of gasoline per ton of bauxite can be obtained sweet to the doctor test. If the catalyst is then regenerated, it is possible to obproduct may be obtained at a low temperature when the bauxite is freshly activated but a higher temperature will be necessary in order to get a completely sweet product at the same flow rate when the catalyst is'old. Decreasing the rate at the lower temperature will produce a sweet gasoline wherein the higher rate would have produced a sour product. In practice the temperature can present in the first four or five volume equivalents,

although the original gasoline vapors contained not a trace of hydrogen sulphide: In' this connection bauxite difiers considerably from adsorbent clays like fullers earth. A sample of 01mstead fullers earthunder similarconditions was found to take up all the hydrogen sulphide until more than 15 liquid volume equivalents of gasoline had been passed over it, and very little hydrogen sulphide was present even in the first 25- volumes.

' The following specific examples are given. as illustrative of the results which have-been obtained on desulphurizing cracked gasoline, but in no sense limit the invention.

Example 1 Gasoline (produced by pressure cracking of Panhandle crude) with sulphur content of 0.156% after removal of hydrogen sulphide was passed over reactivated Arkansas bauxite at'a flow rate of 6.1 barrels of gasoline per hour per ton of bauxite (weight taken on the basis of new ma-.

terial .before dehydration). The temperature ranged from 620 F. atthe beginning to a maxif mum value of 700 F. The following results were obtained:

Barrels oi gaso- Sulphur content line per ton of after removal of Doctor test bauxite H18 0- 97 01087% Sweet. 97-151 0.093% Do. 151-243 0.092% Do. 243-297 Not determined. Do. 297-886 0. 997 Do. 386-443 Not determined. Do. 443-532 0. 101% Do. 1 532-554 Not determined. Very faintly sour.

These results show that even though a gradual increase in sulphur content is obtained the. gasoline remained sweet to doctor until more than 500 barrels of gasoline per ton of bauxite had been desulphurized. The average sulphur reduction 5 was approximately 41.7% based on the origina sulphur content of 0.156%.

Example 2 As stated above, the reactivated bauxite is a 10 more eflicient catalyst for desulphurization than the new material previously dehydrated. A sample of new Arkansas bauxite #3 was dehydrated up to 842 F. while a slow stream of hydrogen gas was passed over it. Gasoline, produced by crack- 15 ing, with 0.183 per centsulphur content (hydrogen sulphide free) was then passed in the vapor phase over this catalyst. The furnace was not equipped with a temperature control so the temperature varied with the line voltage. The flow 0 rates are calculated on barrels of gasoline per hour per ton of new bauxite before dehydration;

Minimum Barrels of and maxi- Sulphur con- 25 gasoline Flow mum temtent after Doctor test per ton of rate perature in removal bauxite agrees, of His Fa enheit a o- 33 as 657-671 0.114% Sweet. 30

33-128 6. 1 657-734 0. 117 Slightly sour. 128-214 6. 0 657-698 0. 123 Sour. 214-266 5.6 684-689 0. 124 Do.

The average sulphur reduction was 34.5% based on the original content of 0.183%. V 35 The above sample of bauxite was then regenerated by the method described above and the following results were then obtained on the same gasoline.

, B 1 1 ii arm 5 0 an max1- gasoline Flow mum temggg i fgggf Doctor per ton of rate perature in of H S test bauxite degrees, 2

. Fahrenheit 7 -oa0 6.0 608-630 Not determined. Sweet W118 I 6.4 630-667 0.106 D0. 118-172 6.75 648-667 0.116 Do. 172-277 6.0 648-684 0.117 Do. 277-298 7. 4 662-684 0. 116 Do.

. The average sulphur reduction was 37.4%. All of the gasoline was sweet to the doctor test, 2.1- though the average working temperature wasconsiderably under that used with the new baux- 55 ite.

Example 3 that of the fullers earth is greatly increased, and

(3) that thebauxite has a greater activity after 5 reactivation than when new, i. e., a larger sulphur reduction is obtained with the result that a completely sweetened gasoline is produced over along period.

Equal weights of new Arkansas bauxite #3 and 70 new Olmstead fullers earth-were placed in tubes side byside in a furnace so that the temperatures of both would be exactly the same at all times during the run, thus eliminating the efiect of fluctuations in furnace temperature. The flow 75 rates in barrels of gasoline per hour per ton of catalyst (hydrated form) were approximately the ,same at all times but the actual contact time of the. vapors was considerably longer in the case of the fullers earth because of its lower specific gravity and, hence, greater volume. If equal volumes insteadof equal weights of the catalysts had been used the superiority of the bauxite would have been greatly increased'over that shown in this example.

A sample of Panhandle cracked gasoline with sulphur content of 0.132% after removal of hydrogen sulphide was used for these tests, the results of which are givenbelow:

New Arkansas bauxite #3 Approxi- Barrels of gasomate mean Sulphur conline per ton of if}: 2312",: tent after Doctor test catalyst d bauxite agrees Fahrenheit 0- 32 9. 1 655 0.084 Sweet. 32- 58 0- 1 545 0. 086 D0. 58-132 6. 0 645 O. 090 Slightly S0111 132-189 6. 2 650 0. 095 Do. 189-274 6. 1 680 O. 095 50111. 274-353 0. 1 685 0. 094 D0. 353-417 5. 9 690 0. 093 DQ. 417-500 5. 9 705 0. 093 D0. 500-559 5. 9 715 D. 097 D0. 559-636 5. 7 725 0. 095 D0. 636-697 5. 8 725 0. 099 D0. 697-780 5. 7 690 0. 106 D0. 730-874 5. 7 710 0. D0. 874-974 5. 9 710 0. D0-

Alggroxi s l h Barrels of gaso- Flow a mean u p peratent after 3 3 g? of rate ture in iullers Doctor test y degrees earth Fahrenheit 0- 25 7. 1 655 0.085 Sweet. 25- 51 6. 1 645 0. 093 D0. 51-125 6. 0 645 0. 095 D0.

-182 6. 2 650 0. 101 SlighUYSOlll 182-266 6. 1 680 0. 100 D0. 266-345 6. 1 685 0. 102 Sour. 845-409 5. 9 6% 0. 102 D0. 409-492 5. 9 705 0. 098 D0. 492-551 5. 9 715 0. 104 D0. 551-622 5. 3 725 0. 102 D0. 622-636 6. 0 725 0. 105 D0. 636-709 5. 7 6m 0. 110 D0. 769-855 5. 2 710 0. 110 D0. 855-952 5. 7 710 0. 116 D0- These catalysts were then regenerated by the method described above and the following results obtained.

Reactivated Arkansas bauxite #3 Approxi- Barrels of gasmm mm Sulphur conoline per ton 2 fi m; am after Doctor an oi catalyst bauxite grees Fahrenheit 0- i2 5. 1 606 0. 077 Sweet. 12- 86 6. 0 617 0. (B4 D0. 86-148 5. 8 630 0. (B6 Do. 148-218 5. 6 644 0. 090 D0. 218-288 5. 7 640 0. 091 D0. 288-351 5. 7 020 0. 097 Faintly sour 351-425 5. 6 655 0. 095 D0.

5. 7 602 0. 094 Very faintly sour. 488-543 5. 8 065 0. 094 Slightly sour 543-624 5. 0 710 0. 091 weet. 624-096 5. 8 700 0. 002 Do. 696-763 6. 6 720 0. 089 Do. 763-4104 s. o 720 o. 091 Do. 804-891 5. 6 no 0. (D2 D0. 891-947 5. 6 730 0. 096 Very slightsour.

ing the hydrogen sulphide, whereby a sweetened Reactwated Olmstead fullers earth apgroxi- S I h Barrels of gas Fl ma mean u p or conow emperatent after gf g g i rate ture in deiuller's w test 5 grees Fahearth renheit 0- 12 5.1 606 0 105 Sweet.

77-134 5.3 630 0 102 Do. 10 134-200 5.4 644 0 101 Slightlysour. 200-269 5.5 640 0 104 Sour.

269- 5. 8 620 0 109 D0. 5.7 655 0 106 Do. 408-471 5.7 662 0 106 Do. 471-526 5.8 665 0 104 Do. 526-608 5. 7 710 0 101 Do. I 608-674 5. 3 700 0. 103 Do. 674-751 6. 4 720 0. 103 D0. 751-794 5. 9 720 0. 099 D0. 794-884 5. 6 730 0. 099 Do. 884-939 5.5 730 0.105 Do.

The average sulphur reductions based on the 50 original sulphur content of 0.132% were:

Per cent New bauxite 25.8 Regenerated bauxite -l. 30.6 25 New fullers earth 21.7 Regenerated fullersearth 22.1

It should be noted that the reactivated bauxitegave a. completely sweetened gasoline far longer than the new bauxite and the fullers earth gave 30 very little sweet gasoline in either case.

Having described the inventioh, what is claimed is: f

1. The method of sweetening mercaptan-bearing petroleum oil with a boiling point lower than 86 the end point of kerosene, comprisingvaporizing the: oil, superheating the resultant vapors to a temperature within the range from 606 to 750 F., passing the superheated vapors, without substantial cooling, through a bed of crushed bauxite 40 catalyst at a fiowrate of about 8 to 20 barrels of oil per hour per ton of catalyst, whereby the mercaptans are converted into hydrogen sulphide, cooling and condensing the vapors, and removoil is obtained.

2. The method ofsweetening mercaptan-bearing petroleum oil with a boiling point lower than the end point of kerosene, comprising vaporizing the oil, superheating the resultant vapors to e50 temperature within therange from 606 to 150 F., contacting thesuperheated vapors, without substantial cooling, with raw dehydrated bauxite for-a period of about 2 to 10 seconds, whereby the mercaptans are converted into hydrogen sulphide, 55 cooling and condensing the vapors, and removing the hydrogen sulphide, whereby a sweetened oil is obtained.

3. The process of sweetening gasoline containing impuritiesof the mercaptan sulphur typefi out substantial cooling with an activated bauxite 75 catalyst for a period of about 2 to 10 seconds, whereby the mercaptans are converted into hydrogen sulphide, cooling and condensing the vapors, and removing the hydrogen sulphide, whereby a sweetened oil is obtained.

5. A cyclic process of sweetening petroleum oil with a boiling point lower than the end point of kerosene, containing impurities of the mercaptan sulphur type, comprising vaporizing the petroleum oil, superheating the vapors to a ternperature within the range from 605 to 750-F., contacting the superheated vapors at.approximately the same temperature with a bauxite catalyst for a period of about 2 to 10 seconds, separating the resultant decomposed sulphur impurities, collecting the petroleum oil sweetened thereby, discontinuing said contacting when a sweet oil is no longer obtained, reactivating the catalyst, and repeating the process.

6. A cyclic process of sweetening gasoline containing impurities of the mercaptan sulphur type, comprising vaporizing the gasoline, superheating the vapors to a temperature within the range from 606 to750 F., contacting the superheated vapors at approximately the same temperature with abauxite catalyst for a period of about 2 to 10 seconds, separating the resultant decomposed 10 sulphur impurities, collecting the gasoline sweetened thereby, discontinuing said contacting when a sweet gasoline is no longer obtained, reactivating the catalyst, and repeating the process. v

ALBERT E. BUELL. WALTER A. SCHULZE. 

